Hydrolysis resistant organomodified disiloxane ionic surfactants

ABSTRACT

An asymmetric organomodified disiloxane surfactant having the formula: MM′ wherein M comprises branched hydrocarbon substituents and M′ comprises a cationic, anionic or zwitterionic substituent and a polyether substituent that may be combined as one moiety, wherein the disiloxane surfactant has an enhanced resistance to hydrolysis between a pH of about 3 to about 12.

FIELD OF THE INVENTION

The present invention relates to disiloxane surfactant compositions thatexhibit resistance to hydrolysis over a wide pH range. More particularlythe present invention relates to such hydrolysis resistant disiloxanesurfactants having a resistance to hydrolysis between a pH of about 3 toa pH of about 12.

BACKGROUND OF THE INVENTION

The topical application of liquid compositions to the surfaces of bothanimate and inanimate objects to effect a desired change involve theprocesses of controlling wetting, spreading, foaming, detergency, andthe like. When used in aqueous solutions to improve the delivery ofactive ingredients to the surface being treated, trisiloxane typecompounds have been found to be useful in enabling the control of theseprocesses to achieve the desired effect. However, the trisiloxanecompounds may only be used in a narrow pH range, ranging from a slightlyacidic pH of 6 to a very mildly basic pH of 7.5. Outside this narrow pHrange, the trisiloxane compounds are not stable to hydrolysis undergoinga rapid decomposition.

SUMMARY OF THE INVENTION

The present invention provides for a silicone composition comprising asilicone having the formula:MM′where

M is selected from the group consisting of R¹R²R³SiO_(1/2);

M′ is selected from the group consisting of R⁴R⁵R⁶SiO_(1/2);

with R¹ selected from the group consisting of branched monovalenthydrocarbon radical of from 3 to 6 carbon atoms and R⁷, where R⁷ isselected from the group consisting ofR⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2))with R⁸, R⁹, and R¹⁰ each independently selected from the group ofmonovalent hydrocarbon radicals having from 1 to 6 carbon atoms andmonovalent aryl or alkaryl hydrocarbon radicals having from 6 to 13carbon atoms and R¹² is a divalent hydrocarbon radical having from 1 to3 carbon atoms;R² and R³ are each independently selected from the group of from 1 to 6carbon atom monovalent hydrocarbon radicals or R¹, where R⁴ isR¹³—R^(A), R¹⁴—R^(C), and R¹⁵—R^(Z);R¹³ is selected from the group

R¹⁸—CHCH₂CH(OH)CH(O—)CH₂CH₂; andR¹⁹O(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)—;where R¹⁶ and R¹⁷ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹⁸ isa divalent hydrocarbon group of 2 to 4 carbon atoms;R¹⁹ is a divalent hydrocarbon group of 1 to 6 carbons, that may each beoptionally branched; subscripts t, u and v are zero or 1;the subscripts a, b and c are zero or positive and satisfy the followingrelationships:1≦a+b+c≦10 with a≧1;R^(A) is a monovalent radical selected from the group consisting of—SO₃M^(K), —C(═O)CH₂CH(R²⁰)COO-M^(K); —PO₃HM^(K); —COOM^(K); where R²⁰is selected from the group consisting of H and —SO₃M^(K); M^(K) is acation selected from the group consisting of Na⁺, K⁺, Ca²⁺, NH₄ ⁺, Li⁺,and monovalent ammonium ions derived from mono-, di- and trialkylaminesof 2 to 4 carbons or mono-, di- and trialkanolamines of 2 to 4 carbons;R¹⁴ is a monovalent radical selected from the group consisting ofR²¹(O)_(w)(R²²)_(x)— andR²³O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₄H₈O)_(f)CH₂CH(OH)CH₂—;where R²¹ and R²² are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R²³ isa divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts w and xare zero or 1; the subscripts d, e and f are zero or positive andsatisfy the following relationships:1≦d+e+f≦10 with d≧1.R^(C) is selected from the group consisting of N(R²⁴)(R²⁵),

where R²⁴ and R²⁵ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R³¹N(R³⁴)(R³⁵), and —R³²O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R³;the subscripts g, h and i are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g≧1.R²⁶, R²⁸, R²⁹, R³⁰ are each independently selected from the groupsconsisting of H and a branched or linear monovalent hydrocarbon radicalof 1 to 4 carbons;R²⁷ is a monovalent radical selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, and—R³⁶O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³⁷;the subscripts j, k and l are zero or positive and satisfy the followingrelationships:1≦j+k+l≦10 with j≧1;R³¹ is a divalent hydrocarbon radical of 1 to 6 carbons, optionallysubstituted with a heterocyclic group containing nitrogen, sulfur,oxygen or combinations thereof orR³⁸O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁹; the subscripts m, n and o arezero or positive and satisfy the following relationships:1≦m+n+o≦10 with m≧1.R³⁴ and R³⁵ are independently selected from the group consisting of Hand a branched or linear monovalent hydrocarbon radical of 1 to 4carbons.R³², R³⁶ and R³⁸ are independently selected from the group consisting ofa divalent hydrocarbon group of 2 to 4 carbon atoms;R³³ is a monovalent radical selected from the group consisting of H, amonovalent hydrocarbon radical of 1 to 6 carbons and N(R⁴⁰)(R⁴¹);R³⁷ and R³⁹ are independently selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, andR⁴²N(R⁴³)(R⁴⁴); where R⁴² is a divalent hydrocarbon radical of 1 to 6carbons. R⁴⁰, R⁴¹, R⁴³ and R⁴⁴ are independently selected from the groupconsisting of H and branched or linear monovalent hydrocarbon radicalsof 1 to 4 carbons;R¹⁵ is a monovalent radical selected from the group consisting ofR⁴⁵(O)_(y)(R⁴⁶)_(z)— andR⁴⁷O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₄H₈O)_(r)CH₂CH(OH)CH₂—; where R⁴⁵ and R⁴⁶are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms, that may each be optionallysubstituted with one or more OH radicals; R⁴⁷ is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts y and z are zero or 1; thesubscripts p, q and r are zero or positive and satisfy the followingrelationships:1≦p+q+r≦10 with p≧1.R^(Z) is —N—(R⁴⁸)(R⁴⁹)_(α)R⁵⁰SO₃(M^(K))_(β),—N—(R⁵¹)(R⁵²)_(γ)R⁵³COO(M^(K))_(δ), N⁺—(R⁵⁴)(R⁵⁵)R⁵⁶OP(═O)(A)(B) or,(—C(═O)N(R⁵⁷)R⁵⁸N—(R⁵⁹)(R⁶⁰))⁺—(R⁶¹OP(is selected from the groupconsisting of O)(A)(B))(X⁻)_(ε);where R⁴⁸, R⁴⁹, R⁵¹, R⁵², R⁵⁴, R⁵⁵, R⁵⁷, R⁵⁹ and R⁶⁰ are independentlyselected from the group consisting of H, a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and an alkanolamine group of 2 to4 carbons;R⁵⁰ is a divalent bridging group of 3 to 4 carbons; subscripts α,β, γand δ are zero or 1 subject to the following relationships: α+β=1 andγ+δ=1;R⁵³ and R⁵⁶ are independently a divalent bridging group of 1 to 4carbons;R⁵⁸ and R⁶¹ are each independently a divalent bridging group of 2 to 4carbons;A and B are selected from O⁻ and OM^(K); X is an anion selected from thegroup of anions consisting of Cl, Br, and I; the subscript ε is 0, 1 or2; andR⁵⁸ and R⁶¹ are each independently a divalent group of 2 to 4 carbons.

The present invention further provides for applications using thecompositions of the present invention in agriculture, personal care,home care, coatings, oil and gas recovery, treatment and processing,water treatment, and pulp and paper processing.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, integer values of stoichiometric subscripts refer tomolecular species and non-integer values of stoichiometric subscriptsrefer to a mixture of molecular species on a molecular weight averagebasis, a number average basis or a mole fraction basis.

As used herein the term emulsion is an inclusive term describingmixtures comprising two or more phases wherein at least one phase isdiscontinuous, regardless of how finely divided that phase may be. Theterm includes, but is not limited to simple emulsions, emulsions withinemulsions, micro-emulsions, macro-emulsions and the like.

The present invention provides for a silicone composition comprising asilicone having the formula:MM′where

M is selected from the group consisting of R¹R²R³SiO_(1/2);

M′ is selected from the group consisting of R⁴R⁵R⁶SiO_(1/2);

with R¹ selected from the group consisting of branched monovalenthydrocarbon radical of from 3 to 6 carbon atoms and R⁷, where R⁷ isselected from the group consisting ofR⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2))with R⁸, R⁹, and R¹⁰ each independently selected from the group ofmonovalent hydrocarbon radicals having from 1 to 6 carbon atoms andmonovalent aryl or alkaryl hydrocarbon radicals having from 6 to 13carbon atoms and R¹² is a divalent hydrocarbon radical having from 1 to3 carbon atoms,

R² and R³ are each independently selected from the group of from 1 to 6carbon atom monovalent hydrocarbon radicals or R¹, where R⁴ isR¹³—R^(A), R¹⁴—R^(C), and R¹⁵—R^(Z);

R¹³ is selected from the group

R¹⁸—CHCH₂CH(OH)CH(O—)CH₂CH₂; andR¹⁹O(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)—;where R¹⁶ and R¹⁷ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹⁸ isa divalent hydrocarbon group of 2 to 4 carbon atoms; R¹⁹ is a divalenthydrocarbon group of 1 to 6 carbons, that may each be optionallybranched; subscripts t, u and v are zero or 1. The subscripts a, b and care zero or positive and satisfy the following relationships:1≦a+b+c≦10 with a≧1.R^(A) is a monovalent radical selected from the group consisting of—SO₃M^(K), —C(═O)CH₂CH(R²⁰)COO⁻M^(K); —PO₃HM^(K); —COOM^(K); where R²⁰is H or —SO₃M^(K); M^(K) is a cation selected from the group consistingof Na⁺, K⁺, Ca²⁺, NH₄ ⁺, Li⁺, and monovalent ammonium ions derived frommono-, di- and trialkylamines of 2 to 4 carbons or mono-, di- andtrialkanolamines of 2 to 4 carbons.R¹⁴ is a monovalent radical selected from the group consisting ofR²¹(O)_(w) (R²²)_(x)— andR²³O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₄H₈O)_(f)CH₂CH(OH)CH₂—;where R²¹ and R²² are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R²³ isa divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts w and xare zero or 1. The subscripts d, e and f are zero or positive andsatisfy the following relationships:1≦d+e+f≦10 with d≧1.R^(C) is selected from N(R²⁴)(R²⁵),

where R²⁴ and R²⁵ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R³¹N(R³⁴)(R³⁵), and —R³²O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R³.The subscripts g, h and i are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g≧1.R²⁶, R²⁸, R²⁹, R³⁰ are each independently selected from the groupsconsisting of H, a branched or linear monovalent hydrocarbon radical of1 to 4 carbons.R²⁷ is a monovalent radical selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, or—R³⁶O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³⁷; the subscripts j, k and l arezero or positive and satisfy the following relationships:1≦j+k+l≦10 with j≧1.R³¹ is a divalent hydrocarbon radical of 1 to 6 carbons, optionallysubstituted with a heterocyclic group containing nitrogen, sulfur,oxygen or combinations thereof orR³⁸O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁹; the subscripts m, n and o arezero or positive and satisfy the following relationships:1≦m+n+o≦10 with m≧1.R³⁴ and R³⁵ are independently selected from the group consisting of H ora branched or linear monovalent hydrocarbon radical of 1 to 4 carbons.R³², R³⁶ and R³⁸ are independently selected from the group consisting ofa divalent hydrocarbon group of 2 to 4 carbon atoms.R³³ is a monovalent radical selected from the group consisting of H, amonovalent hydrocarbon radical of 1 to 6 carbons and N(R⁴⁰)(R⁴¹).R³⁷ and R³⁹ are independently selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, andR⁴²N(R⁴³)(R⁴⁴); where R⁴² is a divalent hydrocarbon radical of 1 to 6carbons. R⁴⁰, R⁴¹, R⁴³ and R⁴⁴ are independently selected from the groupconsisting of H and branched or linear monovalent hydrocarbon radicalsof 1 to 4 carbons.R¹⁵ is a monovalent radical selected from the group consisting ofR⁴⁵(O)_(y)(R⁴⁶)_(z)— andR⁴⁷O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₄H₈O)_(r)CH₂CH(OH)CH₂—; where R⁴⁵ and R⁴⁶are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms, that may each be optionallysubstituted with one or more OH radicals; R⁴⁷ is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts y and z are zero or 1. Thesubscripts p, q and r are zero or positive and satisfy the followingrelationships:1≦p+q+r≦10 with p≧1.R^(Z) is —N—(R⁴⁸)(R⁴⁹)_(α)R⁵⁰SO₃(M^(K))_(β),—N—(R⁵¹)(R⁵²)_(γ)R⁵³COO(M^(K))_(δ), N⁺—(R⁵⁴)(R⁵⁵)R⁵⁶OP(═O)(A)(B) or,(—C(═O)N(R⁵⁷)R⁵⁸N—(R⁵⁹)(R⁶⁰))⁺—(R⁶¹OP(is selected from the groupconsisting of O)(A)(B))(X⁻)_(ε);where R⁴⁸, R⁴⁹, R⁵¹, R⁵², R⁵⁴, R⁵⁵, R⁵⁷, R⁵⁹ and R⁶⁰ are independentlyselected from the group consisting of H, a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and an alkanolamine group of 2 to4 carbons. R⁵⁰ is a divalent bridging group of 3 to 4 carbons;subscripts α, β, γ and δ are zero or 1 subject to the followingrelationships: α+β=1 and γ+δ=1.R⁵³ and R⁵⁶ are independently a divalent bridging group of 1 to 4carbons.R⁵⁸ and R⁶¹ are each independently a divalent bridging group of 2 to 4carbons.A and B are selected from O⁻ and OM^(K); X is an anion selected from thegroup of anions consisting of Cl, Br, and I; the subscript ε is 0, 1 or2.

Particularly useful embodiments of the present invention are exemplifiedby the following choices for species: R¹ is selected from the groupconsisting of isopropyl, iso-butyl, tert-butyl or R⁷, where R⁷ has theformula R⁸R⁹R¹⁰SiR¹² with R⁸, R⁹ and R¹⁰ is selected from the groupconsisting of methyl and R¹² is —CH₂CH₂; R², R³, R⁵, R⁶ is methyl; R¹⁶is —CH₂CH₂CH₂—; R¹⁷ is

—CH₂CH(OH)CH₂—; R¹⁸ is —CH₂CH₂—; R¹⁹ is selected from the groupconsisting of —CH₂CH₂CH₂—, —CH(CH₃)CH₂CH₂—, and —CH₂CH(CH₃)CH₂—;

a, b and c are 0; t is 1, u is 1, v is 0; R²⁰ is H; M^(K) is selectedfrom the group consisting of Na⁺, K⁺ or NH₄ ⁺; R²¹ is selected from thegroup consisting of —CH₂CH₂CH₂—; R²² is CH₂CH(OH)CH₂—; R²³ is—CH₂CH₂CH₂—

d, e, and f is 0; w is 1, x is 1; R²⁴ and R²⁵ is selected from the groupconsisting of H, methyl, ethyl, propyl, isopropyl and

—R³²O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R³³; R³² is —CH₂CH₂CH₂—; g is 1-5,h and i are 0; R³³ is selected from the group consisting of H andmethyl;

R²⁶ and R²⁸ is H; R²⁷ is selected from the group consisting of H, methyland —R³⁶O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³⁷; R³⁶ is selected from thegroup consisting of —CH₂CH₂CH₂—; j is 1-5, k and l are 0; R³⁷ isselected from the group consisting of Hand methyl; R²⁹ and R³⁰ isselected from the group consisting of H;R⁴⁵ is —CH₂CH₂CH₂—; R⁴⁶ is —CH₂CH(CH₃)CH₂—; y and z are 1; R⁴⁷ is—CH₂CH₂CH₂—; p is 1-5, q and r are 0; R⁴⁸ and R⁴⁹ is selected from thegroup consisting of H and methyl; R⁵⁰ is selected from the groupconsisting of —CH₂CH₂CH₂— and —CH₂CH₂CH₂CH₂—; R⁵¹ and R⁵² is eachindependently selected from the group consisting of H and methyl; R⁵³ isselected from the group consisting of —CH₂CH₂CH₂— and —CH₂CH₂CH₂CH₂—;R⁵⁴ and R⁵⁵ are selected from the group consisting of H and methyl; R⁵⁷,and R⁵⁹ and R⁶⁰ are selected from the group consisting of H and methyl.It should be noted that the silicone, MM′, will generally be asymmetric.

One method of producing the composition of the present invention is toreact a molecule of the following formula:MM^(H)where M^(H) is the hydride precursor to the M′ structural unit in thecomposition of the present invention, wherein the definitions andrelationships are later defined and consistent with those defined above,under hydrosilylation conditions, with an olefinically modifiedepoxy-containing moiety, such as allyl glycidyl ether or vinylcyclohexene oxide, which are incorporated here as examples, and not setforth to limit other possible olefinically modified epoxy components,followed by subsequent reaction with an amine-containing group.

Epoxy-modified organofunctional disiloxanes are straightforwardlyprepared through the use of a hydrosilylation reaction to graft theolefinically modified (i.e. vinyl, allyl or methallyl) epoxy group ontothe hydride (SiH) intermediate of the organomodified disiloxane of thepresent invention.

Precious metal catalysts suitable for making epoxy-substituted siloxanesare also well known in the art and comprise complexes of rhodium,ruthenium, palladium, osmium, iridium, and/or platinum. Many types ofplatinum catalysts for this SiH olefin addition reaction are known andsuch platinum catalysts may be used to generate the compositions of thepresent invention. The platinum compound can be selected from thosehaving the formula (PtCl₂Olefin) and H(PtCl₃Olefin) as described in U.S.Pat. No. 3,159,601, hereby incorporated by reference. A further platinumcontaining material can be a complex of chloroplatinic acid with up to 2moles per gram of platinum of a member selected from the classconsisting of alcohols, ethers, aldehydes and mixtures thereof asdescribed in U.S. Pat. No. 3,220,972 hereby incorporated by reference.Yet another group of platinum containing materials useful in thispresent invention is described in U.S. Pat. Nos. 3,715,334; 3,775,452and 3,814,730 (Karstedt). Additional background concerning the art maybe found in J. L. Spier, “Homogeneous Catalysis of Hydrosilation byTransition Metals”, in Advances in Organometallic Chemistry, volume 17,pages 407 through 447, F. G. A. Stone and R. West editors, published byAcademic Press (New York, 1979). Those skilled in the art can easilydetermine an effective amount of platinum catalyst. Generally aneffective amount ranges from about 0.1 to 50 parts per million of thetotal organomodified disiloxane composition.

The compositions of the present invention exhibit an enhanced resistanceto hydrolysis outside a pH range ranging from 6 to 7.5. Enhancedresistance to hydrolysis can be demonstrated by a variety of tests butas used herein enhanced resistance to hydrolysis means 50 mole percentor more of the hydrolysis resistant composition of the present inventionremains unchanged or unreacted after a period of a twenty-four exposureto aqueous acidic conditions where the solution has a pH lower than 6 orafter a period of a twenty-four hour exposure to aqueous basicconditions where the solution has a pH greater than 7.5. Under acidicconditions the compositions of the present invention show a survival of50 mole percent of the original concentration or greater at a pH of 5 orless for a period of time in excess of 48 hours; specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 2weeks; more specifically the compositions of the present invention showa survival of 50 mole percent or greater at a pH of 5 or less for aperiod of time in excess of 1 month; and most specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 6months. Under basic conditions the compositions of the present inventionshow a survival of 50 mole percent or greater at a pH of 8 or more for aperiod of time in excess of 2 weeks; specifically the compositions ofthe present invention show a survival of 50 mole percent or greater at apH of 8 or more for a period of time in excess of 4 weeks; morespecifically the compositions of the present invention show a survivalof 50 mole percent or greater at a pH of 8 or more for a period of timein excess of 6 months; and most specifically the compositions of thepresent invention show a survival of 50 mole percent or greater at a pHof 8 or more for a period of time in excess of 1 year.

USES FOR THE COMPOSITIONS OF THE PRESENT INVENTION

The compositions of the present invention are useful in surfactantapplications. The compositions of the present are useful as surfactantsin a variety of applications. The compositions of the present inventionmay be utilized as pure components, mixtures, or emulsions. As isgenerally known, emulsions comprise at least two immiscible phases oneof which is continuous and the other which is discontinuous. Furtheremulsions may be liquids or gases with varying viscosities or solids.Additionally the particle size of the emulsions may render themmicroemulsions and when sufficiently small microemulsions may betransparent. Further it is also possible to prepare emulsions ofemulsions and these are generally known as multiple emulsions. Theseemulsions may be:

1) aqueous emulsions where the discontinuous phase comprises water andthe continuous phase comprises the composition of the present invention;

2) aqueous emulsions where the discontinuous phase comprises thecomposition of the present invention and the continuous phase compriseswater;

3) non-aqueous emulsions where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises thecomposition of the present invention; and

4) non-aqueous emulsions where the continuous phase comprises anon-aqueous hydroxylic organic solvent and the discontinuous phasecomprises the composition of the present invention.

A. Agricultural Uses

Pesticide—Agriculture, Horticulture, Turf, Ornamental and Forestry:

Many pesticide applications require the addition of an adjuvant to thespray mixture to provide wetting and spreading on foliar surfaces. Oftenthat adjuvant is a surfactant, which can perform a variety of functions,such as increasing spray droplet retention on difficult to wet leafsurfaces, enhance spreading to improve spray coverage, or to providepenetration of the herbicide into the plant cuticle. These adjuvants areprovided either as a tank-side additive or used as a component inpesticide formulations.

Typical uses for pesticides include agricultural, horticultural, turf,ornamental, home and garden, veterinary and forestry applications.

The pesticidal compositions of the present invention also include atleast one pesticide, where the organomodified disiloxane surfactant ofthe present invention is present at an amount sufficient to deliverbetween 0.005% and 2% to the final use concentration, either as aconcentrate or diluted in a tank mix. Optionally the pesticidalcomposition may include excipients, cosurfactants, solvents, foamcontrol agents, deposition aids, drift retardants, biologicals,micronutrients, fertilizers and the like. The term pesticide means anycompound used to destroy pests, e.g., rodenticides, insecticides,miticides, fungicides, and herbicides. Illustrative examples ofpesticides that can be employed include, but are not limited to, growthregulators, photosynthesis inhibitors, pigment inhibitors, mitoticdisrupters, lipid biosynthesis inhibitors, cell wall inhibitors, andcell membrane disrupters. The amount of pesticide employed incompositions of the invention varies with the type of pesticideemployed. More specific examples of pesticide compounds that can be usedwith the compositions of the invention are, but not limited to,herbicides and growth regulators, such as: phenoxy acetic acids, phenoxypropionic acids, phenoxy butyric acids, benzoic acids, triazines ands-triazines, substituted ureas, uracils, bentazon, desmedipham,methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone,norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin,prodiamine, trifluralin, glyphosate, sulfonylureas, imidazolinones,clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl,haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, andbipyridylium compounds.

Fungicide compositions that can be used with the present inventioninclude, but are not limited to, aldimorph, tridemorph, dodemorph,dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole,furconazole, propiconazole, tebuconazole and the like; imazalil,thiophanate, benomyl carbendazim, chlorothialonil, dicloran,trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil,prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin,dodine, and metalaxyl.

Insecticide, larvacide, miticide and ovacide compounds that can be usedwith the composition of the present invention, but not limited to,Bacillus thuringiensis, spinosad, abamectin, doramectin, lepimectin,pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boricacid, chlordimeform, novaluron, bistrifluoron, triflumuron,diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan,dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos,clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrinand the like.

Fertilizers and Micronutrients:

Fertilizers and micronutrients include, but not limited to, zincsulfate, ferrous sulfate, ammonium sulfate, urea, urea ammoniumnitrogen, ammonium thiosulfate, potassium sulfate, monoammoniumphosphate, urea phosphate, calcium nitrate, boric acid, potassium andsodium salts of boric acid, phosphoric acid, magnesium hydroxide,manganese carbonate, calcium polysulfide, copper sulfate, manganesesulfate, iron sulfate, calcium sulfate, sodium molybdate, calciumchloride,

The pesticide or fertilizer may be a liquid or a solid. If a solid, itis preferable that it is soluble in a solvent, or the organomodifieddisiloxanes of the present invention, prior to application, and thesilicone may act as a solvent, or surfactant for such solubility oradditional surfactants may perform this function.

Agricultural Excipients:

Buffers, preservatives and other standard excipients known in the artalso may be included in the composition.

Solvents may also be included in compositions of the present invention.These solvents are in a liquid state at room temperature. Examplesinclude water, alcohols, aromatic solvents, oils (i.e. mineral oil,vegetable oil, silicone oil, and so forth), lower alkyl esters ofvegetable oils, fatty acids, ketones, glycols, polyethylene glycols,diols, paraffinics, and so forth. Particular solvents would be2,2,4-trimethyl, 1-3-pentane diol and alkoxylated (especiallyethoxylated) versions thereof as illustrated in U.S. Pat. No. 5,674,832herein incorporated by reference, or n-methyl-pyrrilidone.

Cosurfactants:

Cosurfactants useful herein include nonionic, cationic, anionic,amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof.Surfactants are typically hydrocarbon based, silicone based orfluorocarbon based.

Moreover, other cosurfactants, that have short chain hydrophobes that donot interfere with superspreading as described in U.S. Pat. No.5,558,806 herein incorporated by reference are also useful.Additionally, the compositions described above are also useful as thealkyl chloride, alkyl iodide and alkyl bromide analogues, as well as theacid pairs with HCl, acetic acid, propionic acid, glycolic acid,gibberellic acid and the like. One skilled in the art understands thebenefits of quaternizernization, which increases solubility and as wellas makes possible potential interactions with nonionic and anioniccosurfactants.

Useful surfactants include alkoxylates, especially ethoxylates,containing block copolymers including copolymers of ethylene oxide,propylene oxide, butylene oxide, and mixtures thereof;alkylarylalkoxylates, especially ethoxylates or propoxylates and theirderivatives including alkyl phenol ethoxylate; arylarylalkoxylates,especially ethoxylates or propoxylates. and their derivatives; aminealkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fattyalcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkylnaphthalene sulfonates; sulfated fatty alcohols, amines or acid amides;acid esters of sodium isethionate; esters of sodium sulfosuccinate;sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acylsarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and soforth.

Specific examples include alkyl acetylenic diols (SURFONYL—AirProducts), pyrrilodone based surfactants (e.g., SURFADONE—LP 100-ISP),2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURF DA530—Rhodia), ethylene diamine alkoxylates (TETRONICS—BASF), ethyleneoxide/propylene oxide copolymers (PLURONICS—BASF), Gemini typesurfactants (Rhodia) and diphenyl ether Gemini type surfactants (e.g.DOWFAX—Dow Chemical).

Preferred surfactants include ethylene oxide/propylene oxide copolymers(EO/PO); amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcoholethoxylates, and so forth.

In a preferred embodiment, the agrochemical composition of the presentinvention further comprises one or more agrochemical ingredients.Suitable agrochemical ingredients include, but not limited to,herbicides, insecticides, growth regulators, fungicides, miticides,acaricides, fertilizers, biologicals, plant nutritionals,micronutrients, biocides, paraffinic mineral oil, methylated seed oils(i.e. methylsoyate or methylcanolate), vegetable oils (such as soybeanoil and canola oil), water conditioning agents such as Choice® (LovelandIndustries, Greeley, Colo.) and Quest (Helena Chemical, Collierville,Tenn.), modified clays such as Surround® (Englehard Corp.), foam controlagents, surfactants, wetting agents, dispersants, emulsifiers,deposition aids, antidrift components, and water.

Suitable agrochemical compositions are made by combining, in a mannerknown in the art, such as, by mixing one or more of the above componentswith the organomodified disiloxane of the present invention, either as atank-mix, or as an “In-can” formulation. The term “tank-mix” means theaddition of at least one agrochemical to a spray medium, such as wateror oil, at the point of use. The term “In-can” refers to a formulationor concentrate containing at least one agrochemical component. The“In-can” formulation may then diluted to use concentration at the pointof use, typically in a Tank-mix, or it may be used undiluted.

B. Coatings:

Typically coatings formulations will require a wetting agent orsurfactant for the purpose of emulsification, compatibilization ofcomponents, leveling, flow and reduction of surface defects.Additionally, these additives may provide improvements in the cured ordry film, such as improved abrasion resistance, antiblocking,hydrophilic, and hydrophobic properties. Coatings formulations mayexists as, Solvent-borne coatings, water-borne coatings and powdercoatings.

The coatings components may be employed as: architecture coatings; OEMproduct coatings such as automotive coatings and coil coatings; SpecialPurpose coatings such as industrial maintenance coatings and marinecoatings;

Typical resin types include: Polyesters, alkyds, acrylics, epoxies

C. Personal Care

In a preferred embodiment, the organomodified disiloxane surfactant ofthe present invention comprises, per 100 parts by weight (“pbw”) of thepersonal care composition, from 0.1 to 99 pbw, more preferably from 0.5pbw to 30 pbw and still more preferably from 1 to 15 pbw of theorganomodified disiloxane surfactant and from 1 pbw to 99.9 pbw, morepreferably from 70 pbw to 99.5 pbw, and still more preferably from 85pbw to 99 pbw of the personal care composition.

The organomodified disiloxane surfactant compositions of the presentinvention may be utilized in personal care emulsions, such as lotions,and creams. As is generally known, emulsions comprise at least twoimmiscible phases one of which is continuous and the other which isdiscontinuous. Further emulsions may be liquids with varying viscositiesor solids. Additionally the particle size of the emulsions may renderthem microemulsions and, when sufficiently small, microemulsions may betransparent. Further it is also possible to prepare emulsions ofemulsions and these are generally known as multiple emulsions. Theseemulsions may be:

1) aqueous emulsions where the discontinuous phase comprises water andthe continuous phase comprises the organomodified disiloxane surfactantof the present invention;

2) aqueous emulsions where the discontinuous phase comprises theorganomodified disiloxane surfactant of the present invention and thecontinuous phase comprises water;

3) non-aqueous emulsions where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises theorganomodified disiloxane surfactant of the present invention; and

4) non-aqueous emulsions where the continuous phase comprises anon-aqueous hydroxylic organic solvent and the discontinuous phasecomprises the organomodified disiloxane surfactant of the presentinvention.

Non-aqueous emulsions comprising a silicone phase are described in U.S.Pat. No. 6,060,546 and U.S. Pat. No. 6,271,295 the disclosures of whichare herewith and hereby specifically incorporated by reference.

As used herein the term “non-aqueous hydroxylic organic compound” meanshydroxyl containing organic compounds exemplified by alcohols, glycols,polyhydric alcohols and polymeric glycols and mixtures thereof that areliquid at room temperature, e.g. about 25° C., and about one atmospherepressure. The non-aqueous organic hydroxylic solvents are selected fromthe group consisting of hydroxyl containing organic compounds comprisingalcohols, glycols, polyhydric alcohols and polymeric glycols andmixtures thereof that are liquid at room temperature, e.g. about 25° C.,and about one atmosphere pressure. Preferably the non-aqueous hydroxylicorganic solvent is selected from the group consisting of ethyleneglycol, ethanol, propyl alcohol, iso-propyl alcohol, propylene glycol,dipropylene glycol, tripropylene glycol, butylene glycol, iso-butyleneglycol, methyl propane diol, glycerin, sorbitol, polyethylene glycol,polypropylene glycol mono alkyl ethers, polyoxyalkylene copolymers andmixtures thereof.

Once the desired form is attained whether as a silicone only phase, ananhydrous mixture comprising the silicone phase, a hydrous mixturecomprising the silicone phase, a water-in-oil emulsion, an oil-in-wateremulsion, or either of the two non-aqueous emulsions or variationsthereon, the resulting material is usually a cream or lotion withimproved deposition properties and good feel characteristics. It iscapable of being blended into formulations for hair care, skin care,antiperspirants, sunscreens, cosmetics, color cosmetics, insectrepellants, vitamin and hormone carriers, fragrance carriers and thelike.

The personal care applications where the organomodified disiloxanesurfactant of the present invention and the silicone compositionsderived therefrom of the present invention may be employed include, butare not limited to, deodorants, antiperspirants,antiperspirant/deodorants, shaving products, skin lotions, moisturizers,toners, bath products, cleansing products, hair care products such asshampoos, conditioners, mousses, styling gels, hair sprays, hair dyes,hair color products, hair bleaches, waving products, hair straighteners,manicure products such as nail polish, nail polish remover, nails creamsand lotions, cuticle softeners, protective creams such as sunscreen,insect repellent and anti-aging products, color cosmetics such aslipsticks, foundations, face powders, eye liners, eye shadows, blushes,makeup, mascaras and other personal care formulations where siliconecomponents have been conventionally added, as well as drug deliverysystems for topical application of medicinal compositions that are to beapplied to the skin.

In a preferred embodiment, the personal care composition of the presentinvention further comprises one or more personal care ingredients.Suitable personal care ingredients include, for example, emollients,moisturizers, humectants, pigments, including pearlescent pigments suchas, for example, bismuth oxychloride and titanium dioxide coated mica,colorants, fragrances, biocides, preservatives, antioxidants,anti-microbial agents, anti-fungal agents, antiperspirant agents,exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts,electrolytes, alcohols, polyols, absorbing agents for ultravioletradiation, botanical extracts, surfactants, silicone oils, organic oils,waxes, film formers, thickening agents such as, for example, fumedsilica or hydrated silica, particulate fillers, such as for example,talc, kaolin, starch, modified starch, mica, nylon, clays, such as, forexample, bentonite and organo-modified clays.

Suitable personal care compositions are made by combining, in a mannerknown in the art, such as, for example, by mixing, one or more of theabove components with the organomodified disiloxane surfactant. Suitablepersonal care compositions may be in the form of a single phase or inthe form of an emulsion, including oil-in-water, water-in-oil andanhydrous emulsions where the silicone phase may be either thediscontinuous phase or the continuous phase, as well as multipleemulsions, such as, for example, oil-in water-in-oil emulsions andwater-in-oil-in water-emulsions.

In one useful embodiment, an antiperspirant composition comprises theorganomodified disiloxane surfactant of the present invention and one ormore active antiperspirant agents. Suitable antiperspirant agentsinclude, for example, the Category I active antiperspirant ingredientslisted in the U.S. Food and Drug Administration's Oct. 10, 1993Monograph on antiperspirant drug products for over-the-counter humanuse, such as, for example, aluminum halides, aluminum hydroxyhalides,for example, aluminum chlorohydrate, and complexes or mixtures thereofwith zirconyl oxyhalides and zirconyl hydroxyhalides, such as forexample, aluminum-zirconium chlorohydrate, aluminum zirconium glycinecomplexes, such as, for example, aluminum zirconium tetrachlorohydrexgly.

In another useful embodiment, a skin care composition comprises theorganomodified disiloxane surfactant, and a vehicle, such as, forexample, a silicone oil or an organic oil. The skin care compositionmay, optionally, further include emollients, such as, for example,triglyceride esters, wax esters, alkyl or alkenyl esters of fatty acidsor polyhydric alcohol esters and one or more the known componentsconventionally used in skin care compositions, such as, for example,pigments, vitamins, such as, for example, Vitamin A, Vitamin C andVitamin E, sunscreen or sunblock compounds, such as, for example,titanium dioxide, zinc oxide, oxybenzone, octylmethoxy cinnamate,butylmethoxy dibenzoylmethane, p-aminobenzoic acid and octyldimethyl-p-aminobenzoic acid.

In another useful embodiment, a color cosmetic composition, such as, forexample, a lipstick, a makeup or a mascara composition comprises theorganomodified disiloxane surfactant, and a coloring agent, such as apigment, a water soluble dye or a liposoluble dye.

In another useful embodiment, the compositions of the present inventionare utilized in conjunction with fragrant materials. These fragrantmaterials may be fragrant compounds, encapsulated fragrant compounds, orfragrance releasing compounds that either the neat compounds or areencapsulated. Particularly compatible with the compositions of thepresent invention are the fragrance releasing silicon containingcompounds as disclosed in U.S. Pat. Nos. 6,046,156; 6,054,547;6,075,111; 6,077,923; 6,083,901; and 6,153,578; all of which are hereinand herewith specifically incorporated by reference.

The uses of the compositions of the present invention are not restrictedto personal care compositions, other products such as waxes, polishesand textiles treated with the compositions of the present invention arealso contemplated.

D. Home Care

Home care applications include laundry detergent and fabric softener,dishwashing liquids, wood and furniture polish, floor polish, tub andtile cleaners, toilet bowl cleaners, hard surface cleaners, windowcleaners, antifog agents, drain cleaners, auto-dish washing detergentsand sheeting agents, carpet cleaners, prewash spotters, rust cleanersand scale removers.

E. Oil and Gas

Compositions of the present organomodified silylated surfactantinvention are useful in oil and gas applications, includingdemulsification.

F. Water Processing

Compositions comprising organomodified silylated surfactant inventionare useful for applications involving commercial and industrial openrecirculating cooling water towers, closed cooling water systems,cooling water conduits, heat exchangers, condensers, once-throughcooling systems, Pasteurizers, air washers, heat exchange systems, airconditioning/humidifiers/dehumidifiers, hydrostatic cookers, safetyand/or fire water protection storage systems, water scrubbers, disposalwells, influent water systems, including filtration and clarifiers,wastewater treatment, wastewater treatment tanks, conduits, filtrationbeds, digesters, clarifiers, holding ponds, settling lagoons, canals,odor control, ion exchange resin beds, membrane filtration, reverseosmosis, micro- and ultra-filtration, assisting in the removal ofbiofilms in cooling tower applications, heat exchangers and processwater systems, and the like.

G. Pulp and Paper

Compositions of the present organomodified silylated surfactantinvention are useful in pulp and paper applications, such as paperboarddefoamers, and wetting agents for the pulping process.

EXPERIMENTAL

The hydride intermediates for the organomodified disiloxane surfactantcompositions of the present invention, as well as comparativecompositions were prepared as described in the following examples.

Preparation Example 1

1,1,3,3-Tetramethyl-3-(3-oxiranylmethoxy-propyl)-1-(2-trimethylsilanyl-ethyl)-disiloxane(FIG. 1). 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (18.8g) and chloroplatininc acid catalyst (ethanolic solution, 30 ppm Pt)were charged to a 100 ml round-bottomed (RB) flask equipped with amagnetic stirrer, reflux condenser, and N₂ inlet. The mixture wasstirred and heated to 90° C. 2-Allyloxymethyl-oxirane (10 g) was placedin an addition funnel and added dropwise to the flask. The mixture wasstirred and maintained at 90° C. for an additional 4 hours. Reactionprogress was followed by NMR spectroscopy. Upon reaction completion,excess 2-allyloxymethyl-oxirane was removed by vacuum distillation.

Preparation Example 2

1-(4-(2-Hydroxy-ethyl)-piperazin-1-yl)-3-(3-(1,1,3,3-tetramethyl-3-(2-trimethylsilanyl-ethyl)-disiloxanyl)-propoxy)-propan-2-ol(FIG. 2). 2-piperazin-1-yl ethanol (0.74 g) and 20 mL of ethanol werecharged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 70° C.1,1,3,3-Tetramethyl-3-(3-oxiranylmethoxy-propyl)-1-(2-trimethylsilanyl-ethyl)-disiloxane(2.0 g) was placed in an addition funnel and added dropwise to theflask. The mixture was stirred and maintained at 70° C. for anadditional 4 hours. The reaction progress was monitored by NMRspectroscopy. Upon reaction completion, ethanol was removed undervacuum, and the mixture was vacuum distilled to remove impurities.

Preparation Example 3

1-(2-(2-Hydroxy-ethoxy)-ethylamino)-3-(3-(1,1,3,3-tetramethyl-3-(2-trimethylsilanyl-ethyl)-disiloxanyl)-propoxy)-propan-2-ol(FIG. 3). 2-(2-Amino-ethoxy)-ethanol (3.02 g) and ethanol (40 mL) werecharged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 70° C.1,1,3,3-Tetramethyl-3-(3-oxiranylmethoxy-propyl)-1-(2-trimethylsilanyl-ethyl)-disiloxane(2.0 g) mixed with ethanol (10 mL) was placed in an addition funnel andadded dropwise to the flask. The mixture was stirred and maintained at70° C. for an additional 4 hours. The reaction progress was monitored byNMR spectroscopy. Upon reaction completion, ethanol was removed undervacuum, and the mixture was vacuum distilled to remove impurities andexcess raw material.

Preparation Example 4

1-(2-(2-(2-Hydroxy-ethoxy)-ethoxy)-ethylamino)-3-(3-(1,1,3,3-tetramethyl-3-(2-trimethylsilanyl-ethyl)-disiloxanyl)-propoxy)-propan-2-ol(FIG. 4). 2-(2-(2-Amino-ethoxy)-ethoxy)-ethanol (4.25 g) and ethanol (40mL) were charged to a 100 mL RB flask equipped with a magnetic stirrer.The mixture was stirred and heated to 70° C.1,1,3,3-Tetramethyl-3-(3-oxiranylmethoxy-propyl)-1-(2-trimethylsilanyl-ethyl)-disiloxane(2.0 g) mixed with ethanol (10 g) was placed in an addition funnel andadded dropwise to the flask. The mixture was stirred and maintained at70° C. for an additional 4 hours. The reaction progress was monitored byNMR spectroscopy. Upon reaction completion, ethanol was removed undervacuum, and the mixture was vacuum distilled to remove impurities andexcess raw material.

Additionally comparative trisiloxane alkoxylates were prepared byconventional methods of platinum mediated hydrosilation, as described inBailey, U.S. Pat. No. 3,299,112, herein incorporated by reference.

Comparative sample A is a trisiloxane ethoxylated surfactant containing8.5 polyoxyethylene repeat units. This product is commercially availableas Silwet® L-77 from Momentive Performance Materials, Wilton, Conn.

Additionally, comparative sample OPE (Octylphenolethoxylate, containing10 polyoxyethylene units) is a non-silicone organic surfactant. Thisproduct is available as Triton® X-100 from Dow Chemical Company,Midland, Mich.

Example 1

This example demonstrates the ability of the organomodified disiloxanesurfactant compositions of the present invention to reduce aqueoussurface tension, thereby showing utility as surfactants. Surface tensionwas measured using pendant drop analysis. Solutions of the variouscomponents were prepared at 0.1 wt % in water (deionized) or 2M NH₄Clsolution.

Table 1 shows that solutions of these unique compositions provide asignificant reduction in surface tension relative to the conventionalsurfactant.

The compositions of the present invention also provide spreadingproperties similar to the comparative trisiloxane surfactant A.Additionally, organomodified disiloxane surfactants of the presentinvention provide improved spreading relative to the conventionalorganic surfactant product OPE.

Spreading was determined by applying a 10 μL droplet, of surfactantsolution to polystyrene Petri dishes (Fisher Scientific) and measuringthe spread diameter (mm) after 30 seconds, at a relative humiditybetween 50 and 70% (at 22 to 25° C.). The solution was applied with anautomatic pipette to provide droplets of reproducible volume. Deionizedwater that was further purified with a Millipore filtration system wasused to prepare the surfactant solutions.

TABLE 1 Surface Tension and Spreading Properties Surface Spread Diameter(mm) Tension 0.1 Weight % Surfactant I.D. (mN/m) DI Water 2M NH₄Cl 221.7 21 10 3 21.6 7 15 4 21.6 45 42 A 20.9 53 nd OPE 31.8 9 nd

Example 2

Unlike traditional siloxane based surfactants, which are subject torapid hydrolysis under acidic and basic conditions (≦15 and ≧pH 9), theorganomodified silylated surfactants of the present invention provideincreased resistance to hydrolysis relative to traditional trisiloxanealkoxylates (Comparative Example A). An artifact of hydrolysis isobserved as a reduction in spreading properties over time. Therefore,solutions of the organomodified silylated surfactants of the presentinvention, as well as comparative surfactants, were prepared at desireduse levels and pH. Spreading was determined as a function of time toillustrate resistance to hydrolysis.

Table 2 is an illustrative example of a traditional organomodifiedtrisiloxane ethoxylate surfactant, which exhibits decreased spreadingperformance with time as a function of hydrolytic decomposition over apH range from pH 3 to pH 10. Here a 0.4 wt % solution of sample A wasprepared at pH 3, 4, 5 and 10. Spreading was determined by applying a 10μL droplet of surfactant solution to polyacetate film (USI, “CrystalClear Write on Film”) and measuring the spread diameter (mm) after 30seconds, at a relative humidity between 50 and 70% (at 22 to 25° C.).The solution was applied with an automatic pipette to provide dropletsof reproducible volume. Deionized water that was further purified with aMillipore filtration system was used to prepare the surfactantsolutions.

TABLE 2 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 3 pH 4 pH 5 pH 10 0 h A 34 28 29 27 1 h A 39 37 2733 2 h A 36 30 33 33 4 h A 41 28 28 29 6 h A 16 27 27 28 8 h A 12 31 2927 24 h A 12 32 25 25 48 h A 10 41 25 33 5 days A 7 30 26 36 7 days A 617 28 25 14 days A 7 7 37 15

Example 3

Table 3 is an illustrative example of an organomodified disiloxanesurfactant of the present invention, where sample 4, a superspreader,has improved resistance to hydrolysis, over a pH range from pH 4 to pH11 relative to a traditional trisiloxane ethoxylate surfactant (ProductA). As mentioned above, resistance to hydrolysis was observed bymonitoring the spreading properties over time. Here a 0.1 wt % solutionof surfactant was prepared in distilled water containing 10 wt. % NaClat pH 4, 5, 9 and 11. Spreading was determined by applying a 10 μldroplet, of surfactant solution to polystyrene Petri dishes (FisherScientific) and measuring the spread diameter (mm) after 30 seconds, ata relative humidity between 50 and 70% (at 22 to 25° C.). The solutionwas applied with an automatic pipette to provide droplets ofreproducible volume.

TABLE 3 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 4 pH 5 pH 9 pH 11 0 h 4 43 44 43 44 24 h 4 43 44 4242 192 h 4 46 45 42 42 2 weeks 4 46 45 41 41 1 month 4 46 45 40 43 2months 4 45 46 42 41

Example 4

Table 4 is an illustrative example of an organomodified disiloxanesurfactant of the present invention, where sample 5, a superspreader,has improved resistance to hydrolysis, over a pH range from pH 4 to pH11 relative to a traditional trisiloxane ethoxylate surfactant (ProductA). As mentioned above, resistance to hydrolysis was observed bymonitoring the spreading properties over time. Here a 0.1 wt % solutionof surfactant was prepared in distilled water containing 10 wt. % NaClat pH 4, 5, 9 and 11. Spreading was determined by applying a 10 μLdroplet, of surfactant solution to polystyrene Petri dishes (FisherScientific) and measuring the spread diameter (mm) after 30 seconds, ata relative humidity between 50 and 70% (at 22 to 25° C.). The solutionwas applied with an automatic pipette to provide droplets ofreproducible volume.

TABLE 4 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 4 pH 5 pH 9 pH 11 0 h 5 18 18 20 21 24 h 5 19 18 2225 192 h 5 19 18 21 24 2 weeks 5 22 20 24 26 1 month 5 19 20 24 24 2months 5 22 23 24 26

The foregoing examples are merely illustrative of the invention, servingto illustrate only some of the features of the present invention. Theappended claims are intended to claim the invention as broadly as it hasbeen conceived and the examples herein presented are illustrative ofselected embodiments from a manifold of all possible embodiments.Accordingly it is Applicants' intention that the appended claims are notto be limited by the choice of examples utilized to illustrate featuresof the present invention. As used in the claims, the word “comprises”and its grammatical variants logically also subtend and include phrasesof varying and differing extent such as for example, but not limitedthereto, “consisting essentially of” and “consisting of.” Wherenecessary, ranges have been supplied; those ranges are inclusive of allsub-ranges there between. Such ranges may be viewed as a Markush groupor groups consisting of differing pairwise numerical limitations whichgroup or groups is or are fully defined by its lower and upper bounds,increasing in a regular fashion numerically from lower bounds to upperbounds. It is to be expected that variations in these ranges willsuggest themselves to a practitioner having ordinary skill in the artand where not already dedicated to the public, those variations shouldwhere possible be construed to be covered by the appended claims. It isalso anticipated that advances in science and technology will makeequivalents and substitutions possible that are not now contemplated byreason of the imprecision of language and these variations should alsobe construed where possible to be covered by the appended claims. AllUnited States patents (and patent applications) referenced herein areherewith and hereby specifically incorporated by reference in theirentirety as though set forth in full.

1. A silicone composition comprising a silicone having the formula:MM′ where M is selected from the group consisting of R¹R²R³SiO_(1/2); M′is selected from the group consisting of R⁴R⁵R⁶SiO_(1/2); with R¹selected from the group consisting of branched monovalent hydrocarbonradical of from 3 to 6 carbon atoms and R⁷, where R⁷ isR⁸R⁹R¹⁰SiR¹² with R⁸, R⁹, and R¹⁰ each independently selected from thegroup of monovalent hydrocarbon radicals having from 1 to 6 carbon atomsand monovalent aryl or alkaryl hydrocarbon radicals having from 6 to 13carbon atoms and R¹² is a divalent hydrocarbon radical having from 1 to3 carbon atoms; R² and R³ are each independently selected from the groupof from 1 to 6 carbon atom monovalent hydrocarbon radicals or R¹, whereR⁴ is R¹³—R^(A), R¹⁴—R^(C) and R¹⁵—R^(Z); R¹³ is selected from the groupconsisting of R¹⁶(O)_(t)(R¹⁷)_(u)(O)_(y)—,

 and R¹⁹O(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)—; where R⁵ and R⁶ are methyl,where R¹⁶ and R¹⁷ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹⁸ isa divalent hydrocarbon group of 2 to 4 carbon atoms; R¹⁹ is a divalenthydrocarbon group of 1 to 6 carbons, that may each be optionallybranched; subscripts t, u and v are zero or 1; the subscripts a, b and care zero or positive and satisfy the following relationships:1≦a+b+c≦10 with a≧1; R^(A) is a monovalent radical selected from thegroup consisting of —SO₃M^(K), —C(═O)CH₂CH(R²⁰)COO⁻M^(K); —PO₃HM^(K);—COOM^(K); where R²⁰ is selected from the group consisting of H and—SO₃M^(K); M^(K) is a cation selected from the group consisting of Na⁺,K⁺, Ca²⁺, NH₄ ⁺, Li⁺, and monovalent ammonium ions derived from mono-,di- and trialkylamines of 2 to 4 carbons or mono-, di- andtrialkanolamines of 2 to 4 carbons; R¹⁴ is a monovalent radical selectedfrom the group consisting of R²¹(O)_(w)(R²²)_(x)— andR²³O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₄H₈O)_(f)CH₂CH(OH)CH₂—; where R²¹ and R²²are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms, that may each be optionallysubstituted with one or more OH radicals; R²³ is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts w and x are zero or 1; thesubscripts d, e and f are zero or positive and satisfy the followingrelationships:1≦d+e+f≦10 with d≧1; R^(C) is selected from the group consisting ofN(R²⁴)(R²⁵),

where R²⁴ and R²⁵ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R³¹N(R³⁴)(R³⁵), and —R³²O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R³;the subscripts g, h and i are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g>1; R²⁶, R²⁸, R²⁹, R³⁰ are each independently selectedfrom the groups consisting of H and a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons; R²⁷ is a monovalent radicalselected from the group consisting of H, a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and—R³⁶O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³⁷; the subscripts j, k and l arezero or positive and satisfy the following relationships:1≦j+k+l≦10 with j≧1; R³¹ is a divalent hydrocarbon radical of 1 to 6carbons, optionally substituted with a heterocyclic group containingnitrogen, sulfur, oxygen or combinations thereof orR³⁸O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁹; the subscripts m, n and o arezero or positive and satisfy the following relationships:1≦m+n+o≦10 with m≧1; R³⁴ and R³⁵ are independently selected from thegroup consisting of H and a branched or linear monovalent hydrocarbonradical of 1 to 4 carbons; R³², R³⁶ and R³⁸ are independently selectedfrom the group consisting of a divalent hydrocarbon group of 2 to 4carbon atoms; R³³ is a monovalent radical selected from the groupconsisting of H, a monovalent hydrocarbon radical of 1 to 6 carbons andN(R⁴⁰)(R⁴¹); R³⁷ and R³⁹ are independently selected from the groupconsisting of H, a branched or linear monovalent hydrocarbon radical of1 to 4 carbons, and R⁴²N(R⁴³)(R⁴⁴); where R⁴² is a divalent hydrocarbonradical of 1 to 6 carbons, R⁴⁰, R⁴¹, R⁴³ and R⁴⁴ are independentlyselected from the group consisting of H and branched or linearmonovalent hydrocarbon radicals of 1 to 4 carbons; R¹⁵ is a monovalentradical selected from the group consisting of R⁴⁵(O)_(y)(R⁴⁶)_(z)— andR⁴⁷O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₄H₈O)_(r)CH₂CH(OH)CH₂—; where R⁴⁵ and R⁴⁶are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms, that may each be optionallysubstituted with one or more OH radicals; R⁴⁷ is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts y and z are zero or 1; thesubscripts p, q and r are zero or positive and satisfy the followingrelationships:1<p+q+r≦10 with p≧1; R^(Z) is selected from the group consisting of—N—(R⁴⁸)(R⁴⁹)_(α)R⁵⁰SO₃(M_(K))_(β), —N—(R⁵¹)(R⁵²)_(y)R⁵³COO(M^(K))_(δ),—N⁺—(R⁵⁴)(R⁵⁵)R⁵⁶OP(═O)(A)(B) and—[—C(═O)N(R⁵⁷)R⁵⁸N⁺(R⁵⁹)(R⁶⁰R⁶¹OP(═O)(A)(B)]X′_(ε) where R⁴⁸, R⁴⁹; R⁵¹;R⁵²; R⁵⁴; R⁵⁵, R⁵⁷, R⁵⁹, and R⁶⁰ are independently selected from thegroup consisting of H, a branched or linear monovalent hydrocarbonradical of 1 to 4 carbons, and an alkanolamine group of 2 to 4 carbons;R⁵⁰ is a divalent bridging group of 3 to 4 carbons; subscripts α, β, γand δ are zero or 1 subject to the following relationships: α+β=1 andγ+δ=1; R⁵³ and R⁵⁶ are independently a divalent bridging group of 1 to 4carbons; R⁵⁸ and R⁶¹ are each independently a divalent bridging group of2 to 4 carbons; A is selected from O⁻ and OM^(K); B is OM^(K); X is ananion selected from the group of anions consisting of Cl, Br, and I; thesubscript ε is 0 or 1; and R⁵⁸ and R⁶¹ are each independently a divalentgroup of 2 to 4 carbons.
 2. The composition of claim 1 where: R¹ isselected from the group consisting of isopropyl, iso-butyl, tert-butyland R⁷; where R⁷ has the formula R⁸R⁹R¹⁰SiR¹² with R⁸, R⁹ and R¹⁰ eachindependently selected from the group consisting of methyl and R¹² is—CH₂CH₂; R², R³, are methyl; R¹⁶ is —CH₂CH₂CH₂—; R¹⁷ is —CH₂CH(OH)CH₂—;R¹⁸ is —CH₂CH₂—; R¹⁹ is selected from the group consisting of—CH₂CH₂CH₂—, —CH(CH₃)CH₂CH₂—, and —CH₂CH(CH₃)CH₂—; R²⁰ is H; M^(K) isselected from the group consisting of Na⁺, K⁺or NH₄ ⁺; R²¹ is selectedfrom the group consisting of —CH₂CH₂CH₂—; R²² is CH₂CH(OH)CH₂—; R²³ is—CH₂CH₂CH₂—; R²⁴ and R²⁵ is selected from the group consisting of H,methyl, ethyl, propyl, isopropyl and—R³²O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R³³; R³² is —CH₂CH₂CH₂—; R³³ isselected from the group consisting of H and methyl; R²⁶ and R²⁸ is H;R²⁷ is selected from the group consisting of H, methyl and—R³⁶O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³⁷; R³⁶ is selected from thegroup consisting of —CH₂CH₂CH₂—; R³⁷ is selected from the groupconsisting of H and methyl; R²⁹ and R³⁰ is selected from the groupconsisting of H; R⁴⁵ is —CH₂CH₂CH₂—; R⁴⁶ is —CH₂CH(CH₃)CH₂—; y and z are1; R⁴⁷ is —CH₂CH₂CH₂—; R⁴⁸ and R⁴⁹ is selected from the group consistingof H and methyl; R⁵⁰ is selected from the group consisting of—CH₂CH₂CH₂— and —CH₂CH₂CH₂CH₂—; R⁵¹ and R⁵² is each independentlyselected from the group consisting of H and methyl; R⁵³ is selected fromthe group consisting of —CH₂CH₂CH₂— and —CH₂CH₂CH₂CH₂—; R⁵⁴ and R⁵⁵ areselected from the group consisting of H and methyl; R⁵⁷, and R⁵⁹ and R⁶⁰are selected from the group consisting of H and methyl.
 3. Thecomposition of claim 2 wherein R⁴ is R¹³—R^(A).
 4. The composition ofclaim 2 wherein R⁴ is R¹⁴—R^(C).
 5. The composition of claim 2 whereinR⁴ is R¹⁵—R^(Z).
 6. An aqueous emulsion where the discontinuous phasecomprises water and the continuous phase comprises the composition ofclaim
 1. 7. An aqueous emulsion where the discontinuous phase compriseswater and the continuous phase comprises the composition of claim
 2. 8.An aqueous emulsion where the discontinuous phase comprises water andthe continuous phase comprises the composition of claim
 3. 9. An aqueousemulsion where the discontinuous phase comprises water and thecontinuous phase comprises the composition of claim
 4. 10. An aqueousemulsion where the discontinuous phase comprises water and thecontinuous phase comprises the composition of claim
 5. 11. An aqueousemulsion where the discontinuous phase comprises the composition ofclaim 1 and the continuous phase comprises water.
 12. An aqueousemulsion where the discontinuous phase comprises the composition ofclaim 2 and the continuous phase comprises water.
 13. An aqueousemulsion where the discontinuous phase comprises the composition ofclaim 3 and the continuous phase comprises water.
 14. An aqueousemulsion where the discontinuous phase comprises the composition ofclaim 4 and the continuous phase comprises water.
 15. An aqueousemulsion where the discontinuous phase comprises the composition ofclaim 5 and the continuous phase comprises water.
 16. A non-aqueousemulsion where the discontinuous phase comprises a non-aqueoushydroxylic solvent and the continuous phase comprises the composition ofclaim
 1. 17. A non-aqueous emulsion where the discontinuous phasecomprises a non-aqueous hydroxylic solvent and the continuous phasecomprises the composition of claim
 2. 18. A non-aqueous emulsion wherethe discontinuous phase comprises a non-aqueous hydroxylic solvent andthe continuous phase comprises the composition of claim
 3. 19. Anon-aqueous emulsion where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises thecomposition of claim
 4. 20. A non-aqueous emulsion where thediscontinuous phase comprises a non-aqueous hydroxylic solvent and thecontinuous phase comprises the composition of claim
 5. 21. A non-aqueousemulsion where the continuous phase comprises a non-aqueous hydroxylicorganic solvent and the discontinuous phase comprises the composition ofclaim
 1. 22. A non-aqueous emulsion where the continuous phase comprisesa non-aqueous hydroxylic organic solvent and the discontinuous phasecomprises the composition of claim
 2. 23. A non-aqueous emulsion wherethe continuous phase comprises a non-aqueous hydroxylic organic solventand the discontinuous phase comprises the composition of claim
 3. 24. Anon-aqueous emulsion where the continuous phase comprises a non-aqueoushydroxylic organic solvent and the discontinuous phase comprises thecomposition of claim
 4. 25. A non-aqueous emulsion where the continuousphase comprises a non-aqueous hydroxylic organic solvent and thediscontinuous phase comprises the composition of claim 5.